WO2020062156A1 - 连续流催化反应器、其组装方法及应用 - Google Patents

连续流催化反应器、其组装方法及应用 Download PDF

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WO2020062156A1
WO2020062156A1 PCT/CN2018/108703 CN2018108703W WO2020062156A1 WO 2020062156 A1 WO2020062156 A1 WO 2020062156A1 CN 2018108703 W CN2018108703 W CN 2018108703W WO 2020062156 A1 WO2020062156 A1 WO 2020062156A1
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continuous flow
reaction container
catalytic reactor
filler
reaction
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PCT/CN2018/108703
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English (en)
French (fr)
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张业新
张建
陈慧
杨杰
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中国科学院宁波材料技术与工程研究所
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Priority to EP18935587.8A priority Critical patent/EP3753632B1/en
Priority to US16/979,532 priority patent/US11033868B2/en
Priority to PCT/CN2018/108703 priority patent/WO2020062156A1/zh
Priority to JP2020544521A priority patent/JP6917661B2/ja
Publication of WO2020062156A1 publication Critical patent/WO2020062156A1/zh

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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
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    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides
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Definitions

  • the present application specifically relates to a continuous flow catalytic reactor, an assembly method and application thereof, such as an application in a monosaccharide epimerization reaction.
  • Continuous flow reaction solves these problems with its unique mixing mode, efficient mass and heat transfer, and low solvent requirements.
  • Continuous flow chemistry or “flow chemistry” refers to the technology of pumping materials through a pump and performing a chemical reaction in a continuous flow mode.
  • the continuous flow reaction in the liquid phase is mostly a catalytic reaction.
  • the catalyst and the raw materials are premixed and then passed to the reactor for reaction. If the catalyst is fixed in the reactor, the catalyst separation step can be saved, the loss of catalyst can be reduced, its utilization efficiency can be improved, and its service life can be extended.
  • Common catalyst fixing methods are physical adsorption and chemical bonding.
  • CN101033192A discloses a continuous flow reaction method for producing mononitrobenzene by nitric nitration of benzene. Metal oxide is supported on a MFI topological molecular sieve and pseudo-boehmite by impregnation, and then pressed into a fixed-bed catalyst; Biggelaar et al.
  • Valence bond ⁇ -transaminase is immobilized on 3-aminopropyltriethoxysilane-modified porous silica for continuous flow reaction of enantioselective transamination (Catalysts, 2017, 7 (54): 1 -13); Et al. Used an ionic bond to immobilize molybdate ions on an anion exchange resin for epimerization of glucose to mannose (Applied Catalysis A, 2008, 334 (1-2): 112-118). In spite of this, the binding force between the catalytically active component and the support is limited, and in a continuous flow reaction, it easily dissolves into the liquid phase medium and loses its activity, resulting in a limited catalyst life.
  • the main purpose of this application is to provide a continuous flow catalytic reactor, its assembly method and application, thereby overcoming the deficiencies in the prior art.
  • An embodiment of the present application provides a continuous-flow catalytic reactor, including a reaction container and a packing enclosed in the reaction container; characterized in that the continuous-flow catalytic reactor further includes a charged catalytic component, and the The catalytic component is fixed on the filler under the action of a DC electric field.
  • the embodiment of the present application further provides an assembly method of the continuous flow catalytic reactor, including:
  • the solution containing the charged catalytic component is input into the reaction container from the liquid flow inlet, it is output from the liquid flow outlet, so that the catalytic component is fixed on the filler.
  • the embodiments of the present application also provide the application of a continuous flow catalytic reactor in a monosaccharide epimerization reaction.
  • the embodiment of the present application further provides a method for epimerizing a monosaccharide, including:
  • the reaction container is heated to a target temperature, and a monosaccharide solution is input from a liquid flow inlet of the reaction container, and a solution containing the target product is collected from a liquid flow outlet of the reaction container.
  • the continuous-flow catalytic reactor of the present application uses a direct-current electric field to fix the charged catalytic component on the filler to form a fixed-bed catalyst.
  • the reaction solution is input at a target temperature, and a reaction occurs under the action of a catalytic component, thereby continuously obtaining a target product.
  • the catalytic components are fixed by the direct current electric field, they will not flow out with the product, which saves the catalyst separation step and improves the utilization efficiency of the catalyst.
  • molybdenum oxide quantum dots or molybdate ions can be used as a catalytic component to achieve a continuous reaction of monosaccharide epimerization.
  • the application of a DC electric field may promote certain chemical reactions that are sensitive to the electric field.
  • FIG. 1 is a schematic structural diagram of a continuous flow catalytic reactor in Embodiment 1 of the present application.
  • a continuous flow catalytic reactor provided in an embodiment of the present application includes a reaction container, a filler packaged in the reaction container, and a charged catalytic component, and the catalytic component is fixed to the component under a DC electric field. On the filler.
  • the reaction vessel is a tubular structure.
  • the reaction container is made of glass, and of course, it can also be made of other materials, such as ceramic, organic, and so on.
  • the filler includes any one or a combination of activated carbon and ion exchange resin, and is not limited thereto.
  • the catalytic component includes a quantum dot, which may be, for example, a molybdenum oxide quantum dot.
  • the catalytic component includes molybdate ions, iron hydroxide colloidal particles, but is not limited thereto.
  • the reaction container has an inner diameter of 1.5 to 2 cm, a length of 50 to 80 cm, and a volume of 100 to 200 ml.
  • the particle size of the filler is 10 to 50 mesh, and the mass-to-volume ratio of the total mass of the filler to the volume of the reaction container is 50 to 120 grams: 100 to 200 milliliters.
  • the voltage of the DC power source for forming the DC electric field is 5-50 volts.
  • An embodiment of the present application further provides an assembly method of any of the foregoing continuous flow catalytic reactors, including:
  • the solution containing the charged catalytic component is input into the reaction container from the liquid flow inlet, it is output from the liquid flow outlet, so that the catalytic component is fixed on the filler.
  • the fiber plug includes glass wool or quartz wool, but is not limited thereto.
  • the filler can be filled into the reaction tube, and the two ends are sealed with glass wool or quartz wool.
  • the middle part of the filler is shorted to the positive or negative electrode of the DC power supply, and the glass wool or quartz wool is shorted to the opposite electrode.
  • a certain volume of the aqueous solution containing the catalytic component is pumped in from one end of the reaction tube, and the other end is pumped out.
  • the voltage of the DC power source is 5-50 volts.
  • the solution containing a charged catalytic component is a quantum dot solution.
  • the concentration of the quantum dot solution is 0.5 to 1 g / liter, and the flow rate is 0.2 to 1 ml / minute.
  • the solution containing the charged catalytic component is a solution containing iron hydroxide colloidal particles or molybdate ions.
  • the embodiment of the present application further provides the application of any of the foregoing continuous flow catalytic reactors to a monosaccharide epimerization reaction.
  • the embodiment of the present application also provides a method for epimerization of a monosaccharide, which includes:
  • the reaction container is heated to a target temperature, and a monosaccharide solution is input from a liquid flow inlet of the reaction container, and a solution containing the target product is collected from a liquid flow outlet of the reaction container.
  • the target temperature is 60-120 ° C.
  • the voltage of the DC power source is 5-50 volts.
  • the monosaccharide solution includes, and is not limited to, any one or more of glucose, mannose, arabinose, ribose, xylose, and lyxose.
  • the concentration of the monosaccharide solution is 1 to 10% by weight.
  • the flow rate of the monosaccharide solution is 0.1 to 2 ml / minute.
  • a charged electric catalytic component is fixed on a filler by using a direct-current electric field to form a fixed-bed catalyst, so that the loss in the continuous-flow reaction can be well suppressed.
  • the continuous flow catalytic reactor of the present application has the advantages of simple structure, unattended operation, safe and convenient operation, and the like.
  • a variety of continuous-flow reactions can be performed.
  • molybdenum oxide quantum dots or molybdate ions can be used as a catalytic component to achieve a continuous reaction of monosaccharide epimerization.
  • the reaction solution is pumped at the target temperature to react with the catalytic components, thereby continuously obtaining the target product.
  • the catalytic components are fixed by the direct current electric field, they will not flow out with the product, which saves the catalyst separation step and improves the utilization efficiency of the catalyst.
  • Embodiment 1 The structure of a continuous flow catalytic reactor in this embodiment is shown in FIG. Among them, the reaction tube 1 is a w-shaped glass material with an inner diameter of 1.8 cm, a length of 70 cm, and a volume of 178 ml.
  • the reaction tube 1 is filled with coconut shell activated carbon filler 2 with a particle diameter of 12-30 mesh and a mass of 80 grams.
  • the two ends of the filler are respectively sealed with quartz cotton 3 and 4; the inlets 7 and 8 are respectively opened near the liquid inlet 5 and the liquid outlet 6.
  • the graphite electrodes 11 and 12 are sealed and fixed with silica gel plugs 9 and 10.
  • the two electrodes penetrate into the reaction tube 1 and are short-circuited with quartz wool 3 and 4 and short-circuited with the negative pole of the DC power source 13. Open 14 in the middle of the reaction tube and use silicone The plug 15 seals and fixes the graphite electrode 16. The electrode penetrates into the reaction tube 1 and is short-circuited with the filler 2, and is short-circuited with the positive electrode of the DC power source 13.
  • Example 2 The reaction tube 1 described in Example 1 was filled with a chloride ion exchange resin filler 2 having a particle size of 20 to 50 mesh and a mass of 100 grams. The two ends of the filler were respectively sealed with glass wool 3 and 4 and connected to a DC power source. Same as in Example 1.
  • Example 3 The reaction tube 1 described in Example 1 was filled with coconut shell activated carbon filler 2 with a particle diameter of 12-30 mesh and a mass of 80 grams. The two ends of the filler are sealed with glass wool 3 and 4 respectively. The connection direction of the positive and negative poles of the DC power supply is opposite to that of Embodiment 1. The glass wool 3 and 4 at both ends of the filler are short-circuited to the positive pole of the power source 13 and the middle portion is short-circuited to the negative pole of the power source 14.
  • Example 4 The reactor of Example 1 was heated by using a water bath method.
  • the reaction tube 1 was immersed in a water bath, and the inlet 5 and the outlet 6 were kept above the water surface, heated to 80 ° C, and the DC power supply 13 was turned on. Maintained at 24 volts; pump the glucose solution from the inlet 5; the mass concentration of the glucose solution was 3%; the flow rate was 0.3 ml / min; and the solution containing the target product mannose was collected from the outlet 6.
  • the reaction was continued for 7 days, and the yield of mannose was maintained at about 23%.
  • Example 5 The reactor of Example 1 was heated by an oil bath method, the reaction tube 1 was immersed in an oil bath, the liquid inlet 5 and the liquid outlet 6 were kept above the oil surface, heated to 90 ° C, and the DC power supply was turned on. 13. The voltage is maintained at 24 volts; the mannose solution is pumped from the inlet 5; the mass concentration of the mannose solution is 1%; the flow rate is 0.1 ml / min; and the solution containing the target product glucose is collected from the outlet 6. The reaction was continued for 7 days, and the yield of glucose was maintained at about 60%.
  • Example 6 The oil-bath method was used to heat the reactor of Example 2.
  • the reaction tube 1 was immersed in an oil bath, and the liquid inlet 5 and the liquid outlet 6 were kept above the oil surface, heated to 100 ° C, and the DC power supply was turned on. 13.
  • the voltage is maintained at 40 volts; the arabinose solution is pumped from the liquid inlet 5, the mass concentration of the arabinose solution is 5%, and the flow rate is 1 ml / min; the solution containing the target product ribose is collected from the liquid outlet 6.
  • the reaction was continued for 3 days, and the yield of ribose was maintained at about 35%.
  • Example 7 The reactor of Example 2 was heated by an oil bath method.
  • the reaction tube 1 was immersed in an oil bath, and the liquid inlet 5 and the liquid outlet 6 were kept above the water surface, heated to 100 ° C, and the DC power supply 13 was turned on.
  • the voltage was maintained at 40 volts; the ribose solution was pumped from the inlet 5 and the mass concentration of the ribose solution was 5%; the flow rate was 1 ml / min; and the solution containing the target product arabinose was collected from the outlet 6.
  • the reaction was continued for 3 days, and the yield of arabinose was maintained at about 62%.
  • Example 8 The reactor of Example 1 was heated by using an oil bath method.
  • the reaction tube 1 was immersed in an oil bath, and the liquid inlet 5 and the liquid outlet 6 were kept above the oil surface, heated to 110 ° C, and the DC power supply was turned on. 13, the voltage is maintained at 10 volts; the xylose solution is pumped from the liquid inlet 5, the mass concentration of the xylose solution is 10%, and the flow rate is 2 ml / min; the solution containing the target product lysose is collected from the liquid outlet 6 .
  • the reaction was continued for 3 days, and the yield of lyxose was maintained at about 30%.
  • Example 9 The reactor of Example 1 was heated by an oil bath method, the reaction tube 1 was immersed in an oil bath, the liquid inlet 5 and the liquid outlet 6 were kept above the oil surface, heated to 120 ° C, and the DC power supply was turned on. 13, the voltage is maintained at 10 volts; the lyxose solution is pumped from the liquid inlet 5, the mass concentration of the lyxose solution is 10%, and the flow rate is 2 ml / min; the target product containing xylose is collected from the liquid outlet 6 Solution. The reaction was continued for 3 days, and the yield of xylose was maintained at about 52%.
  • the initial yield of mannose was about 22%. Due to the loss of molybdenum, after 3 days of reaction, the yield decreased to 3%. (References: Applied Catalysis A, 2008, 334 (1-2): 112-118).
  • the wet catalyst was charged into a 25-ml glass tube with a thermocouple with an electric heater, and was sealed with glass wool at the molten glass to obtain a continuous flow reactor.
  • the initial yield of mannose was about 27%. Due to the loss of molybdenum, after 7 days of reaction, the yield decreased to about 23%. After reaction 33, the yield was reduced to about 12%, and about 1/3 of the molybdenum was lost (Reference: Applied Catalysis A, 2008, 334 (1-2): 112-118).

Abstract

本申请公开了一种连续流催化反应器、其组装方法及应用。所述的连续流催化反应器包括反应容器、封装于所述反应容器内的填料以及带电荷的催化组分，所述催化组分在直流电场作用下被固定于所述填料上。所述的连续流催化反应器可以应用于单糖差向异构化反应等连续流反应。本申请的连续流催化反应器具有结构简单、可无人值守，操作安全方便等优势，且在应用于连续流反应的过程中，由于催化组分被直流电场所固定，不会随产物流出，节省了催化剂的分离步骤，提升了催化剂的利用效率。

Description

连续流催化反应器、其组装方法及应用 技术领域
本申请具体涉及一种连续流催化反应器、其组装方法及应用，例如在单糖差向异构化反应中的应用。
背景技术
传统釜式液相反应解决了大量化工产品需求的问题，但也存在很多自身难以克服的缺点，如安全隐患、环境污染、能源消耗巨大、产品质量不稳定、占地面积大以及工艺放大困难等(化学进展，2016，28(6):829-838)。连续流反应以其独特的混合方式、高效的传质传热、低溶剂需求恰好解决了这些难题。“连续流化学”或称为“流动化学”，是指通过泵输送物料并以连续流动模式进行化学反应的技术。近20年来，连续流反应技术在学术界和工业界越来越受到人们的欢迎，它的优势主要体现在：(1)反应器尺寸小，传质传热迅速，易实现过程强化；(2)参数控制精确，反应选择性好，尤其适合于抑制串联副反应；(3)在线物料量少，微小通道固有阻燃性能，小结构增强装置防爆性能，操作安全；(4)连续化操作，时空效率高；(5)容易实现自动化控制，增强操作的安全性，节约劳动力资源(中国医药工业杂志，2017,48(4)：469-482)。
液相的连续流反应多为催化反应，一般将催化剂与原料预混后通入反应器进行反应。如果将催化剂固定在反应器中，可以节省催化剂分离步骤，减少催化剂的流失，提升其利用效率，延长其使用寿命。常用的催化剂固定方法为物理吸附法和化学成键法。CN101033192A公开了一种硝酸硝化苯生产一硝基苯的连续流反应方法，通过浸渍将金属氧化物负载到MFI拓扑结构分子筛与拟薄水铝石上，然后压制成型为固定床催化剂；Biggelaar等通过共价键将ω-转氨酶通过固定在3-氨丙基三乙氧基硅烷改性的多孔氧化硅上，用于对映选择性氨基转移的连续流反应(Catalysts，2017，7(54)：1-13)；
Figure PCTCN2018108703-appb-000001
等利用离子键将钼酸根离子固定在阴离子交换树脂上，用于葡萄糖到甘露糖的差向异构化反应(Applied CatalysisA，2008，334(1–2)：112-118)。尽管从如此，催化活性组分与载体结合力有限，在连续流反应中易溶进液相介质而损失活性，导致催化剂寿命有限。
发明内容
本申请的主要目的在于提供一种连续流催化反应器、其组装方法及应用，从而克服现有技术中的不足。
为实现前述发明目的，本申请采用的技术方案包括：
本申请实施例提供了一种连续流催化反应器，包括反应容器以及封装于所述反应容器内的填料；其特征在于：所述连续流催化反应器还包括带电荷的催化组分，所述催化组分在直流电场作用下被固定于所述填料上。
本申请实施例还提供了所述连续流催化反应器的组装方法，包括：
将填料装入反应容器，并将反应容器的液流入口和液流出口均以纤维封堵物封堵，所述纤维封堵物可使液流通过但阻挡所述填料；
将所述反应容器的液流入口、液流出口与直流电源的正极或负极电连接，并将所述直流电源的负极或正极与所述填料的中间部分连接；
将包含带电荷的催化组分的溶液自所述液流入口输入反应容器后，再由所述液流出口输出，从而使所述的催化组分被固定在所述填料上。
本申请实施例还提供了连续流催化反应器于单糖差向异构化反应中的应用。
本申请实施例还提供了一种单糖差向异构化反应方法，包括：
提供所述的连续流催化反应器；
将所述的连续流催化反应器与直流电源电连接，从而形成所述的直流电场；以及
将反应容器加热至目标温度，并将单糖溶液自所述反应容器的液流入口输入，再从所述反应容器的液流出口收集包含有目标产物的溶液。
较之现有技术，本申请的连续流催化反应器利用直流电场将带电荷的催化组分固定在填料上，构成固定床催化剂。在目标温度下输入反应溶液，在催化组分的作用下发生反应，进而连续得到目标产物。在此过程中，由于催化组分被直流电场所固定，不会随产物流出，节省了催化剂的分离步骤，提升了催化剂的利用效率。利用该反应器，可以利用氧化钼量子点或钼酸根离子等作为催化组分，实现单糖差向异构化的连续反应。此外，外加直流电场可能会促进某些对电场敏感的化学反应。
附图说明
图1为本申请实施例1中一种连续流催化反应器的结构示意图。
具体实施方式
鉴于现有技术的不足，本案发明人经长期研究和实践，得以提出本申请的技术方案，如下将 予以更为详细的解释说明。
本申请实施例提供的一种连续流催化反应器，包括反应容器、封装于所述反应容器内的填料以及带电荷的催化组分，所述催化组分在直流电场作用下被固定于所述填料上。
在一些实施方式中，所述反应容器为管状结构。
在一些实施方式中，所述反应容器是玻璃材质的，当然也可以为其它材质，例如陶瓷材质、有机材质的，等等。
在一些实施方式中，所述填料包括活性炭、离子交换树脂中的任意一种或两种的组合，且不限于此。
在一些实施方式中，所述催化组分包括量子点，例如可以是氧化钼量子点。
在一些实施方式中，所述催化组分包括钼酸根离子、氢氧化铁胶体粒子，但不限于此。
在一些实施方式中，所述反应容器的内径为1.5～2厘米，长度为50～80厘米，容积为100-200毫升。
在一些实施方式中，所述填料的颗粒尺寸为10～50目，并且所述填料的总质量与所述反应容器的容积的质量体积比为50～120克：100～200毫升。
在一些实施方式中，用于形成所述直流电场的直流电源的电压为5～50伏特。
本申请实施例还提供了前述任一种连续流催化反应器的组装方法，其包括：
将填料装入反应容器，并将反应容器的液流入口和液流出口均以纤维封堵物封堵，所述纤维封堵物可使液流通过但阻挡所述填料；
将所述反应容器的液流入口、液流出口与直流电源的正极或负极电连接，并将所述直流电源的负极或正极与所述填料的中间部分连接；
将包含带电荷的催化组分的溶液自所述液流入口输入反应容器后，再由所述液流出口输出，从而使所述的催化组分被固定在所述填料上。
在一些实施方式中，所述纤维封堵物包括玻璃棉或石英棉等，但不限于此。
在一些较为具体的实施例中，可以将填料装入反应管，两端用玻璃棉或石英棉封堵，填料中间部分短接直流电源正极或负极，两端玻璃棉或石英棉短接相反电极，通电后，将一定体积含催化组分的水溶液从反应管一端泵入，另一端泵出。
在一些实施方式中，所述直流电源的电压为5～50伏特。
在一些实施方式中，所述包含带电荷的催化组分的溶液为量子点溶液。
在一些实施方式中，所述量子点溶液的浓度为0.5～1克/升，流量为0.2～1毫升/分钟。
在一些实施方式中，所述包含带电荷的催化组分的溶液为含有氢氧化铁胶体粒子或钼酸根离子的溶液。
本申请实施例还提供了前述任一种连续流催化反应器于单糖差向异构化反应中的应用。
本申请实施例还提供了一种单糖差向异构化反应方法，其包括：
提供前述的任一种连续流催化反应器；
将所述的连续流催化反应器与直流电源电连接，从而形成所述的直流电场；以及
将反应容器加热至目标温度，并将单糖溶液自所述反应容器的液流入口输入，再从所述反应容器的液流出口收集包含有目标产物的溶液。
在一些实施方式中，所述的目标温度为60～120℃。
在一些实施方式中，所述直流电源的电压为5～50伏特。
在一些实施方式中，所述单糖溶液包含葡萄糖、甘露糖、阿拉伯糖、核糖、木糖和来苏糖中的任意一种或多种的组合，且不限于此。
在一些实施方式中，所述单糖溶液的浓度为1～10wt％。
在一些实施方式中，所述单糖溶液的流量为0.1～2毫升/分钟。
本申请提供的连续流催化反应器中，利用直流电场将带电荷的催化组分固定在填料上，构成固定床催化剂，从而可以很好地抑制其在连续流反应中的流失。
本申请的连续流催化反应器具有结构简单、可无人值守，操作安全方便等优势。利用本申请的连续流催化反应器，可以进行多种的连续流反应，例如，可以以氧化钼量子点或钼酸离子等为催化组分，实现单糖差向异构化的连续反应。在连续流反应过程中，在目标温度下泵入反应溶液，与催化组分作用发生反应，从而连续得到目标产物。其中，由于催化组分被直流电场所固定，不会随产物流出，节省了催化剂的分离步骤，提升了催化剂的利用效率。
下面将结合下面结合附图和实施例来详细说明本申请。需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。
实施例1：本实施例的一种连续流催化反应器的结构如图1所示。其中，反应管1为w型，玻璃材质，内径1.8厘米，长度70厘米，容积178毫升。反应管1内填充椰壳活性炭填料2，粒径12～30目，质量80克，填料两端分别用石英棉3、4封装；在进液口5和出液口6附近分别开口7、8，用硅胶塞9、10密封固定石墨电极11、12；两个电极深入反应管1与石英棉3、4短接，并与直流电源13负极短接；在反应管中间位置开口14，用硅胶塞15密封固定石墨电极16，电极深入反应管1与填料2短接，并与直流电源13正极短接。
准备200毫升氧化钼量子点溶液，浓度为0.8克/升。开通直流电源13，电压保持在24伏特，溶液以0.5毫升/分钟的流量从进液口泵入反应管1，流经填料2，从出液口6处泵出，量子点被电吸附在填料2上，溶液全部流出后得到连续流催化反应器。
实施例2：在实施例1所述反应管1中填充氯离子交换树脂填料2，粒径20～50目，质量100 克，填料两端分别用玻璃棉3、4封装，与直流电源连接方式同实施例1。
准备400毫升钼酸溶液，浓度0.2克/升。开通直流电源13，电压保持在10伏特，溶液以2毫升/分钟的流量从进液口泵入反应管1，流经填料2，从出液口6处泵出，钼酸离子被电吸附在填料2上，得到连续流催化反应器。
实施例3：在实施例1所述反应管1中填充椰壳活性炭填料2，粒径12～30目，质量80克。填料两端分别用玻璃棉3、4封装。直流电源正负极连接方向与实施例1相反，填料两端的玻璃棉3、4短接电源13正极，中间部分短接电源14负极。
准备100毫升氢氧化铁溶胶，浓度2克/升。开通直流电源13，电压保持在50伏特，溶胶以0.2毫升/分钟的流量从进液口泵入反应管1，流经填料2，从出液口6处泵出，氢氧化铁胶体粒子被电吸附在填料2上，得到连续流催化反应器。
实施例4：采用水浴方式对实施例1的反应器加热，将反应管1浸入水浴锅中，进液口5和出液口6保持在水面以上，加热至80℃，开通直流电源13，电压维持在24伏特；从进液口5泵入葡萄糖溶液，葡萄糖溶液的质量浓度为3％，流量为0.3毫升/分钟；从出液口6收集含目标产物甘露糖的溶液。连续反应7天，甘露糖的产率维持在23％左右。
实施例5：采用油浴方式对实施例1的反应器加热，将反应管1浸入油浴锅中，进液口5和出液口6保持在油面以上，加热至90℃，开通直流电源13，电压维持在24伏特；从进液口5泵入甘露糖糖溶液，甘露糖溶液的质量浓度为1％，流量为0.1毫升/分钟；从出液口6收集含目标产物葡萄糖的溶液。连续反应7天，葡萄糖的产率维持在60％左右。
实施例6：采用油浴方式对实施例2的反应器加热，将反应管1浸入油浴锅中，进液口5和出液口6保持在油面以上，加热至100℃，开通直流电源13，电压维持在40伏特；从进液口5泵入阿拉伯糖溶液，阿拉伯糖溶液的质量浓度为5％，流量为1毫升/分钟；从出液口6收集含目标产物核糖的溶液。连续反应3天，核糖的产率维持在35％左右。
实施例7：采用油浴方式对实施例2的反应器加热，将反应管1浸入油浴锅中，进液口5和出液口6保持在水面以上，加热至100℃，开通直流电源13，电压维持在40伏特；从进液口5泵入核糖溶液，核糖溶液的质量浓度为5％，流量为1毫升/分钟；从出液口6收集含目标产物阿拉伯糖的溶液。连续反应3天，阿拉伯糖的产率维持在62％左右。
实施例8：采用油浴方式对实施例1的反应器加热，将反应管1浸入油浴锅中，进液口5和出液口6保持在油面以上，加热至110℃，开通直流电源13，电压维持在10伏特；从进液口5泵入木糖溶液，木糖溶液的质量浓度为10％，流量为2毫升/分钟；从出液口6收集含目标产物来苏糖的溶液。连续反应3天，来苏糖的产率维持在30％左右。
实施例9：采用油浴方式对实施例1的反应器加热，将反应管1浸入油浴锅中，进液口5和 出液口6保持在油面以上，加热至120℃，开通直流电源13，电压维持在10伏特；从进液口5泵入来苏糖溶液，来苏糖溶液的质量浓度为10％，流量为2毫升/分钟；从出液口6收集含目标产物木糖的溶液。连续反应3天，木糖的产率维持在52％左右。
对比例1：250克钼酸钠溶于水，定容至500毫升，加入303克氯离子交换树脂，室温搅拌16小时，加入5滴33％双氧水溶液，用水洗涤过滤固体5次，吸干后滴加1摩尔/升的盐酸调节pH＝3.5，过滤得到湿催化剂。将湿催化剂装入25毫升可电加热具热电偶的玻璃管中，在熔融玻璃处用玻璃棉封装，得到连续流反应器。在90℃以50毫升/小时的流量泵入葡萄糖溶液(质量浓度50％，1摩尔/升的盐酸调节pH＝3.5)进行差向异构化连续流反应。甘露糖的初始产率为22％左右，由于钼流失，反应3天后，产率降至3％。(参考文献：Applied Catalysis A，2008，334(1–2)：112-118)。
对比例2：44.14克钼酸70℃溶于水，定容至500毫升，加入50克氯离子交换树脂，40℃搅拌24小时，滴加1摩尔/升的盐酸调节pH＝3.5，然后用水洗涤过滤固体5次，得到湿催化剂。将湿催化剂装入25毫升可电加热具热电偶的玻璃管中，在熔融玻璃处用玻璃棉封装，得到连续流反应器。在90℃以50毫升/小时的流量泵入葡萄糖溶液(质量浓度50％，1摩尔/升的盐酸调节pH＝3.5)进行差向异构化连续流反应。甘露糖的初始产率为27％左右，由于钼流失，反应7天后，产率降至23％左右。反应33后，产率降至12％左右，大约1/3的钼发生流失(参考文献：Applied Catalysis A，2008，334(1–2)：112-118)。
此外，本案发明人还参照实施例1-9的方式，以本说明书中列出的其它原料和条件等进行了试验，并同样利用本申请的连续流催化反应器成功应用于连续流反应。
上述实例只为说明本申请的技术构思及特点，其目的在于让熟悉此项技术的人是能够了解本申请的内容并据以实施，并不能以此限制本申请的保护范围。凡根据本申请精神实质所做的等效变换或修饰，都应涵盖在本申请的保护范围之内。

Claims (10)

  1. 一种连续流催化反应器，包括反应容器以及封装于所述反应容器内的填料；其特征在于：所述连续流催化反应器还包括带电荷的催化组分，所述催化组分在直流电场作用下被固定于所述填料上。
  2. 根据权利要求1所述的连续流催化反应器，其特征在于：所述反应容器为管状结构；和/或，所述反应容器是玻璃材质的；和/或，所述填料包括活性炭、离子交换树脂中的任意一种或两种的组合；和/或，所述催化组分包括量子点，所述的量子点包括氧化钼量子点；或者，所述催化组分包括钼酸根离子或氢氧化铁胶体粒子。
  3. 根据权利要求2所述的连续流催化反应器，其特征在于：所述反应容器的内径为1.5～2厘米，长度为50～80厘米，容积为100-200毫升；和/或，所述填料的颗粒尺寸为10～50目，并且所述填料的总质量与所述反应容器的容积的质量体积比为50～120克：100～200毫升。
  4. 根据权利要求1所述的连续流催化反应器，其特征在于：用于形成所述直流电场的直流电源的电压为5～50伏特。
  5. 如权利要求1-4中任一项所述连续流催化反应器的组装方法，其特征在于包括：
    将填料装入反应容器，并将反应容器的液流入口和液流出口均以纤维封堵物封堵，所述纤维封堵物可使液流通过但阻挡所述填料；
    将所述反应容器的液流入口、液流出口与直流电源的正极或负极电连接，并将所述直流电源的负极或正极与所述填料的中间部分连接；
    将包含带电荷的催化组分的溶液自所述液流入口输入反应容器后，再由所述液流出口输出，从而使所述的催化组分被固定在所述填料上。
  6. 如权利要求5所述的组装方法，其特征在于：所述纤维封堵物包括玻璃棉或石英棉。
  7. 如权利要求5所述的组装方法，其特征在于：所述直流电源的电压为5～50伏特；和/或，所述包含带电荷的催化组分的溶液为量子点溶液，所述量子点溶液的浓度为0.5～1克/升，流量为0.2～1毫升/分钟；或者，所述包含带电荷的催化组分的溶液为含有钼酸根离子或氢氧化铁胶体粒子的溶液。
  8. 如权利要求1-4中任一项所述连续流催化反应器于单糖差向异构化反应中的应用。
  9. 一种单糖差向异构化反应方法，其特征在于包括：
    提供如权利要求1-4中任一项所述的连续流催化反应器；
    将所述的连续流催化反应器与直流电源电连接，从而形成所述的直流电场；以及
    将反应容器加热至目标温度，并将单糖溶液自所述反应容器的液流入口输入，再从所述反应 容器的液流出口收集包含有目标产物的溶液。
  10. 如权利要求9所述的单糖差向异构化反应方法，其特征在于：所述的目标温度为60～120℃；和/或，所述直流电源的电压为5～50伏特；和/或，所述单糖溶液包含葡萄糖、甘露糖、阿拉伯糖、核糖、木糖和来苏糖中的任意一种或多种的组合；和/或，所述单糖溶液的浓度为1～10wt％；和/或，所述单糖溶液的流量为0.1～2毫升/分钟。
PCT/CN2018/108703 2018-09-29 2018-09-29 连续流催化反应器、其组装方法及应用 WO2020062156A1 (zh)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033192A (zh) 2006-03-06 2007-09-12 北京夏一催化技术有限公司 一种硝酸硝化苯生产一硝基苯的方法
WO2011133536A1 (en) * 2010-04-19 2011-10-27 The University Of Toledo Aldose-ketose transformation for separation and/or chemical conversion of c6 and c5 sugars from biomass materials
CN204503034U (zh) * 2015-02-13 2015-07-29 凌一洲 高效催化管
CN108452793A (zh) * 2017-02-17 2018-08-28 中国科学院宁波材料技术与工程研究所 一种单糖差向异构化反应催化剂

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3714473A1 (de) * 1987-04-30 1988-11-10 Basf Ag Kontinuierliches verfahren zur epimerisierung von zuckern, insbesondere von d-arabinose zu d-ribose
US4815445A (en) * 1988-02-09 1989-03-28 Allied-Signal Inc. Solid catalysts for epimerization of aldoses; continuous interconversion of epimeric sugars
ZA200209011B (en) * 2001-11-20 2003-05-26 Rohm & Haas Electroactive catalysis.
US7087147B2 (en) * 2001-11-20 2006-08-08 Rohm And Haas Company Electroactive catalysis
US7371327B2 (en) * 2005-03-04 2008-05-13 Kenneth Cross Device for the immobilization of nano- and micro-sized particles in a solid-fluid contact vessel facilitating mass-momentum, and heat-transport at the solid-fluid interfaces
US9962651B2 (en) * 2011-09-21 2018-05-08 Nbc Meshtec, Inc. Device and method for gas treatment using non-thermal plasma and catalyst medium
WO2014160321A2 (en) * 2013-03-14 2014-10-02 Ed Chen Method and apparatus for the electrical activation of a catalyst
WO2018148939A1 (zh) * 2017-02-17 2018-08-23 中国科学院宁波材料技术与工程研究所 一种单糖差向异构化反应催化剂

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033192A (zh) 2006-03-06 2007-09-12 北京夏一催化技术有限公司 一种硝酸硝化苯生产一硝基苯的方法
WO2011133536A1 (en) * 2010-04-19 2011-10-27 The University Of Toledo Aldose-ketose transformation for separation and/or chemical conversion of c6 and c5 sugars from biomass materials
CN204503034U (zh) * 2015-02-13 2015-07-29 凌一洲 高效催化管
CN108452793A (zh) * 2017-02-17 2018-08-28 中国科学院宁波材料技术与工程研究所 一种单糖差向异构化反应催化剂

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
APPLIED CATALYSIS A, vol. 334, no. 1-2, 2008, pages 112 - 118
CATALYSTS, vol. 7, no. 54, 2017, pages 1 - 13
CHINESE JOURNAL OF PHARMACEUTICAL INDUSTRY, vol. 48, no. 4, 2017, pages 469 - 482
KOCKRITZ ET AL.: "fixed molybdate ions on anion exchange resin by ion bonds to be used for epimerization from glucose to mannose", APPLIED CATALYSIS A, vol. 334, no. 1-2, 2008, pages 112 - 118
PROGRESS IN CHEMISTRY, vol. 28, no. 6, 2016, pages 829 - 838
See also references of EP3753632A4

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